EP1876141B1 - Stable high-temperature borohydride formulation - Google Patents

Stable high-temperature borohydride formulation Download PDF

Info

Publication number
EP1876141B1
EP1876141B1 EP07252555A EP07252555A EP1876141B1 EP 1876141 B1 EP1876141 B1 EP 1876141B1 EP 07252555 A EP07252555 A EP 07252555A EP 07252555 A EP07252555 A EP 07252555A EP 1876141 B1 EP1876141 B1 EP 1876141B1
Authority
EP
European Patent Office
Prior art keywords
borohydride
sodium
sbh
acrylic acid
alternatively
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
EP07252555A
Other languages
German (de)
French (fr)
Other versions
EP1876141A2 (en
EP1876141A3 (en
Inventor
Curtis Schwartz
John Hiroshi Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of EP1876141A2 publication Critical patent/EP1876141A2/en
Publication of EP1876141A3 publication Critical patent/EP1876141A3/en
Application granted granted Critical
Publication of EP1876141B1 publication Critical patent/EP1876141B1/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
    • C01B6/15—Metal borohydrides; Addition complexes thereof
    • C01B6/19—Preparation from other compounds of boron
    • C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention relates to an aqueous sodium borohydride mixture having increased stability, especially at high temperatures.
  • Aqueous borohydride solutions having relatively good stability are known. For example, solutions containing about 12% sodium borohydride and about 40% sodium hydroxide are sold commercially. In some applications, a stable borohydride-containing solution having less sodium hydroxide is desired, e.g., in hydrogen fuel cells. Such a solution is described in U.S. Pat. No. 6,866,689 ; it contains about 44% sodium borohydride and about 0.2% sodium hydroxide. However, this solution exhibits relatively high rates of borohydride decomposition at elevated temperatures.
  • US-A-3 933 676 discloses borohydride with the inorganic excipient sodium zincate.
  • the problem addressed by this invention is to find an aqueous formulation of borohydride that has improved stability at elevated temperatures.
  • the present invention provides an aqueous mixture comprising: (a) from 15% to 65% of at least one borohydride compound; (b) from 1% to 10% of at least one metal hydroxide; and (c) from 0.1% to 20% of at least one absorbent polymer or excipient.
  • the invention is further directed to a method for stabilizing aqueous borohydride mixtures by adding at least one absorbent polymer.
  • a "borohydride compound” is a compound containing the borohydride anion, BH 4 -.
  • An "absorbent polymer” is a polymer capable of absorbing water.
  • absorbent polymers are chosen from among water-soluble polymers (polymers having water solubility of at least 1%, alternatively at least 5%), cellulose and its derivatives, and cross-linked polymers.
  • Cross-linked polymers preferably have carboxyl, amide, hydroxy, amino, or ether groups, or a combination thereof, to facilitate dispersion in water.
  • Excipients are pharmaceutical excipients as defined, e.g., in Handbook of Pharmaceutical Excipients, A.
  • preferred absorbent polymers include polyacrylic acids, polyacrylamide co polyacrylic acid, copolymers of acrylic acid (e.g., polyacrylic acid co polyethylene oxide), polyvinylpyrrolidone, polyvinylpyridine, polyvinylpyridine N-oxide, polyvinylimidazole, ethoxylated polyethylenimine, cellulose esters (e.g., acetate, butyrate), hydroxyalkyl celluloses, and carboxymethyl cellulose.
  • the aqueous mixture of the present invention may be a solution, slurry, gel, or any other fluid mixture at temperatures of at least 40°C. Mixtures having higher concentrations of borohydride, e.g., at least 50%, typically are solids or thick slurries at ambient temperature of about 25°C, but become fluid at higher temperatures.
  • the amount of borohydride compound(s) is at least 20%, alternatively at least 25%. In one embodiment, the amount of metal hydroxide(s) is no more than 8%, alternatively no more than 6%, alternatively no more than 4%. In one embodiment of the invention, the amount of metal hydroxide is at least 2%, alternatively at least 3%. In one embodiment, the amount of borohydride compound is no more than 55%, alternatively no more than 50%, alternatively no more than 45%, alternatively no more than 40%.
  • the borohydride compound is a metal salt which has a metal cation from groups 1, 2, 4, 5, 7, 11, 12 or 13 of the periodic table, or a mixture thereof.
  • the borohydride compound is an alkali metal borohydride or combination thereof, alternatively it comprises sodium borohydride (SBH) or potassium borohydride or a mixture thereof, alternatively sodium borohydride.
  • the metal hydroxide is an alkali metal hydroxide or combination thereof; alternatively sodium, lithium or potassium hydroxide, or a mixture thereof; alternatively sodium hydroxide or potassium hydroxide; alternatively sodium hydroxide. More than one alkali metal borohydride and more than one metal hydroxide may be present.
  • the amount of absorbent polymer(s) is at least 0.2%, alternatively at least 0.4%, alternatively at least 1%, alternatively at least 2%. In one embodiment of the invention, the amount of absorbent polymer(s) is no more than 15%, alternatively no more than 12%, alternatively no more than 10%, alternatively no more than 8%. In one embodiment of the invention, extremely small amounts of absorbent polymer(s) are required; at least 0.1%, but no more than 1%, alternatively no more than 0.5%.
  • partially neutralized polyacrylic acids or copolymers containing at least 20% acrylic acid monomer units, alternatively at least 30%, alternatively at least 50%, alternatively at least 75%, may require only very small amounts of absorbent polymer(s) and/or excipient(s).
  • the degree of neutralization of the polyacrylic acids added to the borohydride compound(s) is not critical because the aqueous mixture contains additional base, so that the acids typically will be completely neutralized in the aqueous mixture.
  • a weight average molecular weight of at least 1500 is preferred, alternatively at least 3000, alternatively at least 5000.
  • the aqueous mixture is substantially free of substances that catalyze hydrolysis of borohydride, e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
  • borohydride e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
  • the aqueous mixture of this invention also may be used in the fields of synthesis and metal recovery.
  • poly acrylic acid partial cross linked partial sodium salt to higher-concentration sodium borohydride formulations also results in decreasing the hydrolysis rates of the 40 and 50 wt % formulations.
  • An unexpected phenomenon has been observed when these formulations are heated for long periods of time. After an initial induction period, the rate of hydrolysis of the borohydride decreases to nearly zero.
  • Table 3 Decomposition rate of solutions containing 50 % SBH, 5 % NaOH with additives at room temperature and 58 °C 50 % SBH, 5 %

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Fuel Cell (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  • This invention relates to an aqueous sodium borohydride mixture having increased stability, especially at high temperatures.
  • Aqueous borohydride solutions having relatively good stability are known. For example, solutions containing about 12% sodium borohydride and about 40% sodium hydroxide are sold commercially. In some applications, a stable borohydride-containing solution having less sodium hydroxide is desired, e.g., in hydrogen fuel cells. Such a solution is described in U.S. Pat. No. 6,866,689 ; it contains about 44% sodium borohydride and about 0.2% sodium hydroxide. However, this solution exhibits relatively high rates of borohydride decomposition at elevated temperatures.
  • US-A-3 933 676 discloses borohydride with the inorganic excipient sodium zincate.
  • The problem addressed by this invention is to find an aqueous formulation of borohydride that has improved stability at elevated temperatures.
    • STATEMENT OF INVENTION
  • The present invention provides an aqueous mixture comprising: (a) from 15% to 65% of at least one borohydride compound; (b) from 1% to 10% of at least one metal hydroxide; and (c) from 0.1% to 20% of at least one absorbent polymer or excipient. The invention is further directed to a method for stabilizing aqueous borohydride mixtures by adding at least one absorbent polymer.
    • DETAILED DESCRIPTION
  • Percentages are weight percentages and temperatures are in °C, unless specified otherwise. A "borohydride compound" is a compound containing the borohydride anion, BH4-. An "absorbent polymer" is a polymer capable of absorbing water. Preferably, absorbent polymers are chosen from among water-soluble polymers (polymers having water solubility of at least 1%, alternatively at least 5%), cellulose and its derivatives, and cross-linked polymers. Cross-linked polymers preferably have carboxyl, amide, hydroxy, amino, or ether groups, or a combination thereof, to facilitate dispersion in water. "Excipients" are pharmaceutical excipients as defined, e.g., in Handbook of Pharmaceutical Excipients, A. Wade & P.J. Weller (1964). In one embodiment of the invention, preferred absorbent polymers include polyacrylic acids, polyacrylamide co polyacrylic acid, copolymers of acrylic acid (e.g., polyacrylic acid co polyethylene oxide), polyvinylpyrrolidone, polyvinylpyridine, polyvinylpyridine N-oxide, polyvinylimidazole, ethoxylated polyethylenimine, cellulose esters (e.g., acetate, butyrate), hydroxyalkyl celluloses, and carboxymethyl cellulose. The aqueous mixture of the present invention may be a solution, slurry, gel, or any other fluid mixture at temperatures of at least 40°C. Mixtures having higher concentrations of borohydride, e.g., at least 50%, typically are solids or thick slurries at ambient temperature of about 25°C, but become fluid at higher temperatures.
  • In one embodiment, the amount of borohydride compound(s) is at least 20%, alternatively at least 25%. In one embodiment, the amount of metal hydroxide(s) is no more than 8%, alternatively no more than 6%, alternatively no more than 4%. In one embodiment of the invention, the amount of metal hydroxide is at least 2%, alternatively at least 3%. In one embodiment, the amount of borohydride compound is no more than 55%, alternatively no more than 50%, alternatively no more than 45%, alternatively no more than 40%. Preferably, the borohydride compound is a metal salt which has a metal cation from groups 1, 2, 4, 5, 7, 11, 12 or 13 of the periodic table, or a mixture thereof. In one embodiment, the borohydride compound is an alkali metal borohydride or combination thereof, alternatively it comprises sodium borohydride (SBH) or potassium borohydride or a mixture thereof, alternatively sodium borohydride. Preferably, the metal hydroxide is an alkali metal hydroxide or combination thereof; alternatively sodium, lithium or potassium hydroxide, or a mixture thereof; alternatively sodium hydroxide or potassium hydroxide; alternatively sodium hydroxide. More than one alkali metal borohydride and more than one metal hydroxide may be present.
  • In one embodiment of the invention, the amount of absorbent polymer(s) is at least 0.2%, alternatively at least 0.4%, alternatively at least 1%, alternatively at least 2%. In one embodiment of the invention, the amount of absorbent polymer(s) is no more than 15%, alternatively no more than 12%, alternatively no more than 10%, alternatively no more than 8%. In one embodiment of the invention, extremely small amounts of absorbent polymer(s) are required; at least 0.1%, but no more than 1%, alternatively no more than 0.5%. For example, partially neutralized polyacrylic acids, or copolymers containing at least 20% acrylic acid monomer units, alternatively at least 30%, alternatively at least 50%, alternatively at least 75%, may require only very small amounts of absorbent polymer(s) and/or excipient(s). The degree of neutralization of the polyacrylic acids added to the borohydride compound(s) is not critical because the aqueous mixture contains additional base, so that the acids typically will be completely neutralized in the aqueous mixture. For polymers used in this invention, a weight average molecular weight of at least 1500 is preferred, alternatively at least 3000, alternatively at least 5000.
  • In one embodiment of the invention, the aqueous mixture is substantially free of substances that catalyze hydrolysis of borohydride, e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
  • The aqueous mixture of this invention also may be used in the fields of synthesis and metal recovery.
    • EXAMPLES
  • Table 1: Decomposition rate of solutions containing 25% SBH, 3% NaOH with additives at room temperature and 60 °C.
    25% SBH, 3% NaOH with Additive Wt % of additive Rate of decomposition At RT, %SBH/day Rate of decomposition at 60 °C %SBH/day % decrease in decomposition rate at 60 °C
    None, 25 % NaBH4 , 3 % NaOH N/A -0.12 -0.958 N/A
    Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 -0.05 -0.564 41
    Poly acrylamide co acrylic acid partial sodium salt (solid) Mw=15,000,000 0.5 -0.074 -0.662 31
    Poly acrylic acid co poly ethylene oxide (solid) CAS # 27599-59-56-0 0.5 -0.012 -0.614 36
    Poly vinyl pyrrolidone (solid) Mw=10,000; CAS # 9003-39-0 0.5 -0.004 -0.734 23
    Carboxy methyl cellulose sodium salt (solid) Mw=70,000; CAS # 9004-39-4 0.5 -0.032 -0.728 24
  • The addition of poly acrylic acid partial cross linked partial sodium salt to higher-concentration sodium borohydride formulations also results in decreasing the hydrolysis rates of the 40 and 50 wt % formulations. An unexpected phenomenon has been observed when these formulations are heated for long periods of time. After an initial induction period, the rate of hydrolysis of the borohydride decreases to nearly zero. Table 2: Decomposition rate ("DR") of solutions containing 40 % SBH, 5 % NaOH with additives at room temperature and 50°C
    40 % SBH, 5 % NaOH with Additive Wt % of additive DR at RT %SBH/day DR at 50 °C %SBH/Day % decrease in DR at 50 °C DR at 50 °C %SBH/Day After induction period
    None, 40 % NaBH4 , 5 % NaOH N/A 0.0549 0.3604 N/A N/A
    Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 0.0333 0.1139 68 0.0547
    Poly acrylic acid partial sodium salt (Liquid) Mw= 30,000; CAS # 9003-04-07 4% 0.0339 0.1716 52 0.0084
    Table 3: Decomposition rate of solutions containing 50 % SBH, 5 % NaOH with additives at room temperature and 58 °C
    50 % SBH, 5 % NaOH with Additive Wt % of additive DR at RT %SBH/day DR at 58°C %SBH/day % decrease in DR DR at 58 °C %SBH/day after induction period
    None, 50 % NaBH4, 5 % NaOH N/A 0.0031 0.35 N/A N/A
    Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 % - 0.03121 91 0.01165
    Poly acrylic acid partial sodium salt (Liquid) Mw= 30,000; CAS # 9003-04-07 4 % - 0.01715 95 0.01388
    Table 4: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly acrylic acid), partial sodium salt solid at 22 °C.
    Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference
    22 0 0.026 N/A
    22 0.5 0.011 57.7
    22 1 0.0485
    22 1.5 0.0473
    22 2 0.0473
    22 4 0.025 3.8
    Table 5: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly acrylic acid), partial sodium salt solid at 60 °C.
    Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference
    60 0 0.4334 N/A
    60 0.5 0.3764 13.2
    60 1 0.409 5.6
    60 1.5 0.424 2.1
    60 2 0.4114 5.1
    60 4 0.4201 3.1
    Table 6: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly (acrylic acid sodium salt 30 % in water Mw=15,000 at 22 °C. (wt.% additive in this table, and following tables based on total polymer/water formulation)
    Temp °C Wt % additive Rate of decomposition, % SBH/Day Rate of decomposition of standard, % SBH/Day % Difference
    22 0
    22 10 0.1161 0.0114
    22 5 0.0019 0.1029 98.1
    22 1 0.046 0.0421
    Table 7: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of polyacrylic acid sodium salt 30 % in water Mw=15,000 at 60 °C
    Temp °C Wt% additive Rate of decomposition, % SBH/Day Rate of decomposition of standard, % SBH/Day % Difference
    60 0
    60 10 0.3982 0.4993 20.2
    60 5 0.4301 0.4964 13.3
    60 1 0.4236 0.4399 3.7
    Table 8: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of polyethyleneimine 80 % ethoxylated at 22 °C
    Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference
    Standard 0 0.0585 N/A
    22 Polyethylenimine 80 %, ethoxylated, 37 % in water Mw= 50,000; CAS # 26558-46-8 15 0.0116 80.1
    22 Polyethylenimine 80 % ethoxylated, 35 to 40 % in water Mw= 70,000; CAS # 26558-46-8 15 0.0321 45.1
    Table 9: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of polyethyleneimine 80 % ethoxylated at 60 °C
    Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference
    Standard 0 0.5782 N/A
    60 Polyethyleneimine 80 % ethoxylated, 37 % in water M w= 50,000; CAS # 26558-46-8 15 0.5096 11.8
    60 Polyethylenimine 80 % ethoxylated , 35 to 40 % in water Mw= 70,000; CAS # 26558-46-8 15 0.5052 12.6
    Table 10: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of different MW polyacrylic acid sodium salts at 22 °C
    Temp °C Wt % additive DR %SBH/Day % Difference
    Standard 0 0.0585 N/A
    22 Poly (acrylic acid sodium salt 45 % in water Mw= 1,200; CAS # 9003- 04-7 15 0.06493 Higher by 10
    22 Poly (acrylic acid sodium salt 45 % in water Mw= 8,000; CAS # 9003-04-7 15 0.0257 56.0
    22 Poly (acrylic acid sodium salt 40 % in water Mw= 30,000; CAS # 9003-04-7 15 0.0091 84.4
    Table 11: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of different MW poly acrylic acid sodium salts at 60°C
    Temp °C Wt % additive DR %SBH/Day % Difference
    Standard 0 0.5782 N/A
    60 Poly (acrylic acid sodium salt 45 % in water M w= 1,200; CAS # 9003-04-7 15 0.3812 34.0
    60 Poly (acrylic acid sodium salt 45 % in water M w= 8,000; CAS # 9003-04-7 15 0.3607 37.6
    60 Poly (acrylic acid sodium salt 40 % in water M w= 30,000; CAS # 9003-04-7 15 0.3736 35.38

Claims (10)

  1. An aqueous mixture comprising:
    (a) from 15% to 65% of at least one borohydride compound;
    (b) from 1% to 10% of at least one metal hydroxide; and
    (c) from 0.1% to 20% of at least one absorbent polymer.
  2. The aqueous mixture of claim 1 in which said at least one borohydride compound is sodium borohydride, potassium borohydride or a combination thereof; and said at least one metal hydroxide is sodium, lithium or potassium hydroxide, or a combination thereof.
  3. The aqueous mixture of claim 2 in which said at least one absorbent polymer is selected from among water-soluble polymers, cellulose and its derivatives and crosslinked polymers.
  4. The aqueous mixture of claim 3 in which the borohydride compound is sodium borohydride and the base is sodium hydroxide.
  5. The aqueous mixture of claim 4 having from 2% to 8% sodium hydroxide and from 20% to 50% sodium borohydride.
  6. The aqueous mixture of claim 5 in which said at least one absorbent polymer is polyacrylic acid or a copolymer of acrylic acid having at least 50% acrylic acid monomer units.
  7. The aqueous mixture of claim 6 having from 0.1 % to 1% polyacrylic acid or acrylic acid copolymer, and in which weight average molecular weight of the polyacrylic acid or copolymer of acrylic acid is at least 1500.
  8. A method for stabilizing an aqueous borohydride mixture containing from 15% to 65% of at least one borohydride compound and from 1% to 10% of at least one metal hydroxide; said method comprising adding from 0.1 % to 20% of at least one absorbent polymer.
  9. The method of claim 8 in which said at least one metal hydroxide is sodium hydroxide and said at least one borohydride compound is sodium borohydride.
  10. The method of claim 9 in which the aqueous borohydride mixture has from 2% to 8% sodium hydroxide and from 20% to 50% sodium borohydride.
EP07252555A 2006-07-05 2007-06-22 Stable high-temperature borohydride formulation Expired - Fee Related EP1876141B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US81860906P 2006-07-05 2006-07-05

Publications (3)

Publication Number Publication Date
EP1876141A2 EP1876141A2 (en) 2008-01-09
EP1876141A3 EP1876141A3 (en) 2008-01-23
EP1876141B1 true EP1876141B1 (en) 2010-12-01

Family

ID=38577433

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07252555A Expired - Fee Related EP1876141B1 (en) 2006-07-05 2007-06-22 Stable high-temperature borohydride formulation

Country Status (7)

Country Link
US (1) US7648644B2 (en)
EP (1) EP1876141B1 (en)
JP (1) JP4883794B2 (en)
KR (2) KR20080004355A (en)
CN (1) CN101100286B (en)
CA (1) CA2592655C (en)
DE (1) DE602007010867D1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633492B (en) * 2008-07-22 2013-02-27 汉能科技有限公司 Solid hydroboron hydrogen production method and device thereof
KR101245914B1 (en) * 2010-12-21 2013-03-20 황보창수 Processing device of a dried cuttlefish
US20170158390A1 (en) * 2015-12-04 2017-06-08 Mead Johnson Nutrition Company Powder dosing closure
JP2019026753A (en) * 2017-07-31 2019-02-21 株式会社ブリヂストン Aldehyde scavenger for polyurethane, polyurethane and method for producing polyurethane

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970114A (en) * 1958-01-27 1961-01-31 Metal Hydrides Inc Stabilized aqueous solutions of sodium borohydride
DE1567554A1 (en) * 1966-04-02 1970-07-09 Goerrig Dipl Chem Dr Rer Nat D Solids containing alkali hydroxide hydrate, alkali boronate and optionally catalysts
US3933676A (en) * 1974-04-08 1976-01-20 Ventron Corporation Stabilized aqueous solutions of sodium borohydride
US5169555A (en) * 1990-11-09 1992-12-08 Morton International, Inc. Pulp bleaching solution
US5354478A (en) * 1993-06-09 1994-10-11 Morton International, Inc. Alkali metal borohydride/anionic polymer solutions
FR2746328B1 (en) * 1996-03-21 1998-05-29 Stmi Soc Tech Milieu Ionisant ORGANOMINERAL DECONTAMINATION GEL AND ITS USE FOR THE DECONTAMINATION OF SURFACES
JP2001019401A (en) * 1999-07-05 2001-01-23 Seijiro Suda Hydrogen generating agent and hydrogen generating method utilizing the same
JP2002201001A (en) * 2000-12-28 2002-07-16 Toyota Motor Corp Stabilization method for metal complex hydride water solution
JP2003146604A (en) * 2001-11-08 2003-05-21 Sekisui Chem Co Ltd Compression molding for hydrogen generation and method and device for generating hydrogen using the same
US6866689B2 (en) * 2001-11-13 2005-03-15 Montgomery Chemicals, Llc. Aqueous borohydride compositions
JP2004196634A (en) * 2002-12-20 2004-07-15 Honda Motor Co Ltd Hydride powder used for hydrogen storing/discharging system
JP4276854B2 (en) * 2003-01-30 2009-06-10 ウチヤ・サーモスタット株式会社 Hydrogen generating material, hydrogen generating method and hydrogen generating apparatus
CN100384736C (en) * 2004-10-18 2008-04-30 罗门哈斯公司 Method for reducing corrosion in solid sodium hydroxide production
JP4813790B2 (en) * 2004-12-03 2011-11-09 セイコーインスツル株式会社 Hydrogen generator and fuel cell system

Also Published As

Publication number Publication date
KR101113732B1 (en) 2012-02-27
CN101100286A (en) 2008-01-09
CA2592655C (en) 2011-04-19
JP4883794B2 (en) 2012-02-22
US7648644B2 (en) 2010-01-19
US20080009575A1 (en) 2008-01-10
KR20080004355A (en) 2008-01-09
JP2008013431A (en) 2008-01-24
EP1876141A2 (en) 2008-01-09
CN101100286B (en) 2011-11-16
KR20090051152A (en) 2009-05-21
CA2592655A1 (en) 2008-01-05
DE602007010867D1 (en) 2011-01-13
EP1876141A3 (en) 2008-01-23

Similar Documents

Publication Publication Date Title
EP1876141B1 (en) Stable high-temperature borohydride formulation
CA2576588C (en) Method for generation of hydrogen gas from borohydride
JP5150604B2 (en) Generation method of hydrogen gas
RU2008103482A (en) COMPOSITION AND MEDICINAL FORM CONTAINING A SOLID OR SEMI-SOLID MATRIX
JP2009143975A (en) Solid electrolyte material
US10081060B2 (en) Method of forming silver nanoparticles and a use thereof
CA2796168A1 (en) Acetaminophen composition
Tako et al. Synergistic interaction between agarose and D-galacto-D-mannan in aqueous media
CA2576585C (en) Borohydride fuel formulation
JP2008050298A (en) External gel composition for attachment to skin
KR100828702B1 (en) A method of producing hydrogen using amino acids
JP2007335119A (en) Solid electrolyte material
JP6598377B2 (en) Alumina colloid-containing aqueous solution
CN110812769A (en) Environment-friendly anti-solubility aqueous film-forming foam extinguishing agent and preparation method thereof
JP4313382B2 (en) Vinylpyrrolidone polymer composition
KR100596367B1 (en) Hydrogen generating composition
CN112739383B (en) Peroxide-stable polymer compositions, process for their preparation and their use
US4212886A (en) Stabilized benactyzine hydrochloride
JP4162482B2 (en) High molecular weight vinyl lactam polymer and process for producing the same
Devi et al. Development of polyelectrolyte complex microparticles for the encapsulation of isoniazid
WO2007114301A1 (en) Stabilizer for composition containing water-soluble polymer thickener
JP2018162232A (en) Covered chlorine agent tablet and chlorine agent tablet package
Ebube Preformulation studies of matrix-type sustained release tablets.
JPH11349773A (en) Stabilization of acrylamide polymer
JPH0343300B2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 20070705

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17Q First examination report despatched

Effective date: 20080306

AKX Designation fees paid

Designated state(s): DE FR GB IT

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602007010867

Country of ref document: DE

Date of ref document: 20110113

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20110902

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602007010867

Country of ref document: DE

Effective date: 20110902

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20140618

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20140606

Year of fee payment: 8

Ref country code: DE

Payment date: 20140618

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20140609

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602007010867

Country of ref document: DE

Representative=s name: MUELLER-BORE & PARTNER PATENTANWAELTE PARTG MB, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602007010867

Country of ref document: DE

Representative=s name: MUELLER-BORE & PARTNER PATENTANWAELTE PARTG MB, DE

Effective date: 20150408

Ref country code: DE

Ref legal event code: R081

Ref document number: 602007010867

Country of ref document: DE

Owner name: VERTELLUS PERFORMANCE CHEMICALS LLC, INDIANAPO, US

Free format text: FORMER OWNER: ROHM AND HAAS CO., PHILADELPHIA, PA., US

Effective date: 20150408

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602007010867

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150622

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150622

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150622

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150630